Abstract
Cation-induced dimerization of nickel(II), platinum(II), and palladium(II) meso-tetra(benzo-15-crown-5)porphyrinates (Ni(II)TCP, Pd(II)TCP, and Pt(II)TCP) on treatment with potassium thiocyanate in a chloroform-methanol solution has been studied by electronic absorption spectroscopy. The formation of [{MTCP}2(K+)4](SCN−)4 in solution induces a hypsochromic shift of the Soret band and a bathochromic shift of the β-band with respect to their positions in the spectrum of MTCP. The equilibrium constants (K) for the 2MTCP + 4K+ = [{MTCP}2(K+)4] processes at 20°C are determined to be as follows: log KNi(II)TCP = 27.31 ± 1.67, logKPd(II)TCP = 27.16 ± 1.43, and logKPt(II)TCP = 26.15 ± 1.56.
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